Phenyl ketone derivatives

ABSTRACT

Compounds of the formula I, II or III ##STR1## in which Ar and Ar&#39; are an oxygen-containing aromatic radical, R 1  and R 2  are a monovalent hydrocarbon radical which is substituted or unsubstituted, or R 1  and R 2  together form alkylene, oxaalkylene or azaalkylene, R 3  is a direct bond or a divalent hydrocarbon radical, X and X&#39; are a monovalent amino group and Y is a divalent amino or diamino group, are excellent photoinitiators for the photocuring of colored, especially pigmented, compositions containing an olefinically unsaturated, photopolymerizable binder.

This is a divisional of application Ser. No. 579,622 filed on Feb. 13,1984, now U.S. Pat. No. 4,559,371.

The invention relates to photocurable coloured compositions containingan olefinically unsaturated binder, a pigment or a dye and a specificphotoinitiator. The photoinitiator is an aromatic-aliphatic ketone whichcontains, in the aromatic moiety, one or more hydroxyl or ether groupsand contains, in the aliphatic moiety, a tertiary α-C atom on which anamino group is located.

It is known that photoinitiators are added before irradiation in orderto accelerate the photocuring of coloured compositions, for exampleprinting inks or paints. This renders it possible to cure suchcompositions in a very short time of irradiation sufficiently for theirsurface to be no longer tacky. Whereas there are a number of technicallysatisfactory photoinitiators for transparent coating compositions, theradiation curing of coloured compositions constitutes a problemparticularly difficult to solve because of the presence of thelight-absorbing pigments or dyes. In the case of printing inks there isalso the requirement for extremely short curing times because of thehigh speed of modern printing machines. The requirements forphotoinitiators for coloured compositions are therefore considerablyhigher than those for transparent photocurable compositions.

Photoinitiators which have hitherto been used in the art for the curingof such coloured compositions, for example printing inks or paints, arein most cases synergistic mixtures of ketonic photoinitiators withspecific amines, for example a mixture of benzophenone with Michler'sketone (4,4'-bis-dimethylaminobenzophenone) or with alkylp-dimethylaminobenzoates, or mixtures of thioxanthones withN-methyldiethanolamine. Ketone-amine mixtures of this type tend toundergo yellowing in light. This can manifest itself as early as theradiation curing, but at the latest when the cured layers are exposed tothe prolonged action of light. Some of these compounds are difficultlysoluble in the customary acrylic resin binders, then to recrystalliseand considerably shorten the storage life of the mixture. Othercompounds of this type, for example the alkanolamines, are soluble inwater and therefore cannot be used for wet offset printing inks.Furthermore, the ketone-amine mixtures act in accordance with abimolecular initiation mechanism which is controlled by diffusion andtherefore takes place relatively slowly in systems of high viscosity.

Molecular combinations of aryl ketones and amines in which the aminogroup is located on a tertiary C atom in the α-position in relation tothe carbonyl group have already been suggested as photoinitiators inEuropean Patent Application, Publication No. 3002. However, theaminoketones described in this text have proved inferior asphotoinitiators in clear lacquers to the corresponding hydroxyketonesdescribed in the same patent specification. The hydroxyketones describedin this text are admittedly excellent initiators for transparentlacquers, but exhibit only a moderately good action in pigmentedcompositions, for example in printing inks.

It has been found that such aminoketones which carry at least onehydroxyl or ether group on the aromatic nucleus surprisingly exhibit anexcellent initiator action in coloured compositions, especially inprinting inks, and do not have the disadvantages of the ketone-aminemixtures or have these disadvantages to a considerably lesser extent.

The invention relates therefore to photocurable coloured compositionscontaining:

(a) an olefinically unsaturated, photopolymerisable binder,

(b) a pigment or a dye and

(c) as photoinitiator, at least one compound of the formula I, II or III##STR2## in which Ar is an oxygen-containing aromatic radical, selectedfrom the following formulae: ##STR3## wherein n is 1, 2 or 3,

Z is a direct bond, --CH₂ --, --CH₂ CH₂ -- or --O--,

Z' is 13 CH₂ CH₂ -- or --(CH₂)₃, each unsubstituted or substituted byCH₃,

R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one another are each hydrogen,halogen, C₁ -C₄ -alkyl, C₃ -C₁₂ -alkenyl, C₅ -C₆ -cycloalkyl, phenyl,--COOH, --COO(C₁ -C₄ -alkyl), --OH or --OR⁹, with the proviso howeverthat at least one of the radicals R⁴ to R⁸ is an --OH or --OR⁹ group,

R⁹ is C₁ -C₁₂ -alkyl, C₃ -C₁₂ -alkenyl, cyclohexyl, hydroxycyclohexyl,C₁ -C₄ -alkyl which is substituted by one or more of the groups Cl, Br,CN, SH, --N(C₁ -C₄ -alkyl)₂, piperidino, morpholino, OH, --O(C₁ -C₄-alkyl), --OCH₂ CH₂ CN, --OCH₂ CH₂ COO(C₁ -C₄ -alkyl), --OOC--R¹⁰,--COOH, --COO(C₁ -C₈ -alkyl), --CONH(C₁ -C₄ -alkyl), --CON(C₁ -C₄-alkyl)₂, ##STR4## --CO--(C₁ -C₄ -alkyl) or --CO--phenyl, or is2,3-epoxypropyl, --(CH₂ CH₂ O)_(q) --H, phenyl, C₇ -C₉ -phenylalkyl, C₇-C₉ -phenylhydroxyalkyl, phenyl which is substituted by halogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy or --COO(C₁ -C₄ -alkyl), or is tetrahydropyranyl,tetrahydrofuranyl, a group --CO--R¹⁰, --COO(C₁ -C₈ -alkyl), --CONH(C₁-C₄ -alkyl), --CON(C₁ -C₄ -alkyl)₂, --Si(R¹⁵)(R¹⁶)₂, --SO₂ --R¹⁷ or aradical of the formula ##STR5## wherein p is 1 to 4, q is 2 to 20, A isoxygen or sulfur and B is a direct bond or a C₁ -C₁₀ -alkylene radical,or R₉ is a radical of the formula ##STR6## R¹⁰ is C₁ -C₄ -alkyl, C₂ -C₄-alkenyl or phenyl, X and X' are each an amino group --N(R¹¹)(R¹²),

Y is a divalent radical of the formula ##STR7## --N(R¹³)-- or--N(R¹³)--(CH₂)_(x) --N(R^(13'))--, wherein x is 1 to 8,

R¹¹ is hydrogen, C₁ -C₁₂ -alkyl, C₂ -C₄ -alkyl which is substituted byone or more of the groups OH, C₁ -C₄ -alkoxy, CN or --COO(C₁ -C₄-alkyl), or is C₃ -C₅ -alkenyl, cyclohexyl, C₇ -C₉ -phenylalkyl, phenylor phenyl substituted by Cl, C₁ -C₄ -alkyl, OH, C₁ -C₄ -alkoxy or--COO(C₁ -C₄ -alkyl), or R¹¹ and R¹ together are the group --CH₂ OCH₂--,

R¹² has one of the meanings given for R¹¹ or together with R¹¹ is C₃ -C₇-alkylene which can be interrupted by --O--, --S-- or --N(R¹⁴)--, or R¹²together with R² is C₁ -C₈ -alkylene, C₇ -C₁₀ -phenylalkylene,o-xylylene or C₂ -C₄ -oxa or azaalkylene,

R¹³ and R^(13') are hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₄ -hydroxyalkyl,cyclohexyl or benzyl,

R¹⁴ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -hydroxyalkyl, --CH₂ CH₂ CN or--CH₂ CH₂ COO(C₁ -C₄ -alkyl),

R¹⁵ and R¹⁶ are C₁ -C₄ -alkyl or phenyl,

R¹⁷ is C₁ -C₁₈ -alkyl, phenyl or C₇ -C₂₀ -alkylphenyl,

Ar' has one of the meanings given for Ar,

R¹ and R² independently of one another are each C₁ -C₈ -alkyl, C₁ -C₄-alkyl which is substituted by OH, C₁ -C₄ -alkoxy, CN, --COO(C₁ -C₈-alkyl) or --N(R¹¹)(R¹²), or are allyl, phenyl, chlorophenyl, R⁹--O--phenyl or C₇ -C₉ -phenylalkyl, or R¹ and R² together are C₂ -C₈-alkylene, C₃ -C₉ -oxa- or azaalkylene,

R³ is a direct bond, C₁ -C₆ -alkylene, C₂ -C₆ -oxaalkylene orcyclohexylene, or together with the two substituents R² and the two Catoms to which they are attached forms a cyclopentane, cyclohexane,cyclohexene, endomethylenecyclohexane or endomethylenecyclohexene ring,

or to an acid addition salt of such a compound.

As alkyl, R⁹ can be therein straight-chain or branched-chain alkyl, forexample: methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl,isoamyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl.

As alkenyl, R⁹ can be in particular alkenyl-methyl, for example allyl,methallyl or 11-undecenyl.

As substituted alkyl, R⁹ can be for example: 2-chloroethyl,2-bromomethyl, 3-chloropropyl, cyanomethyl, 2-cyanoethyl,2-mercaptoethyl, dimethylaminomethyl, morpholinomethyl,2-piperidinoethyl, 2-morpholinoethyl, 2-hydroxyethyl, 2-hydroxypropyl,2-butoxyethyl, 2-ethoxybutyl, 2-(2'-cyanoethoxy)-propyl,2-(2'-ethoxycarbonylethoxy)-ethyl, 2-acetoxyethyl), 2-acryloyloxypropyl,2-benzoyloxyethyl, carboxymethyl, 2-methoxycarbonylethyl,butoxycarbonylmethyl, n-octyloxycarbonylmethyl, 2-diethylcarbamoylethyl,morpholinocarbonylmethyl, 2-isobutyroylethyl, 2-benzoylethyl oracetylmethyl.

When R⁹ is phenylalkyl or phenylhydroxyalkyl, this can be for example:benzyl, phenylethyl, phenylpropyl or 2-phenyl-2-hydroxyethyl.

R⁹ as substituted phenyl can be for example: 4-chlorophenyl,3-bromophenyl, 2-fluorophenyl, p-tolyl, p-isopropylphenyl,2,4-dimethylphenyl, 4-methoxyphenyl, 3-ethoxy-p-tolyl,3-methoxycarbonylphenyl or 4-butoxycarbonyl-phenyl.

X can be a primary, secondary or tertiary amino group; preferablyhowever X is a tertiary amino group. The substituents R¹¹ and R¹² can bealiphatic, cycloaliphatic aromatic or araliphatic groups. Examples ofR¹¹ and R¹² are the groups: methyl, ethyl, propyl, butyl, hexyl, octyl,2-ethylhexyl, dodecyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl,2-methoxypropyl, 2-ethoxyethyl, 2-cyanoethyl, 2-methoxycarbonylethyl,ethoxycarbonylmethyl, 2-isopropoxycarbonylethyl, allyl, methallyl,cyclohexyl, benzyl, phenylethyl, phenyl, 4-chlorophenyl, 4-tolyl,3-hydroxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl,4-methoxycarbonyl-phenyl or 2,4-dimethylphenyl. When R¹¹ and R¹²together are alkylene or interrupted alkylene, X can be for example: apyrrolidino, oxazolidino, piperidino, 3,5-dimethylpiperidino,morpholino, 3,5-dimethyl-morpholino, thiomorpholino, piperazino,4-methylpiperazino, 4-(cyanoethyl)-piperazino or4-(hydroxyethyl)piperazino group. When R¹² together with R² forms analkylene, phenylalkylene, o-xylylene, oxaalkylene or azaalkyleneradical, these can form, together with the C atom to which R² and R¹²are attached, for example an aziridine, pyrrolidine, piperidine,tetrahydroisoquinoline, phenylaziridine, methylpyrrolidine,dimethylpiperidine or morpholine ring. When R¹¹ and R¹ together are--CH₂ OCH₂ --, these radicals together with the nitrogen atom and thequaternary carbon atom form an oxazolidine ring. If R¹² and R² also forman oxazolidine ring of this type, this results in compounds of theformula ##STR8## X is preferably a morpholino radical or a radical ofthe formula --N(CH₂ CH₂ OCH₃)₂. Y is a divalent secondary or tertiaryamino or diamino group. Examples of diamino groups --N(R¹³)--(CH₂)_(x)--N(R^(13'))-- are in particular those in which x=1, 2, 3, 4 and 6. AsC₁ -C₁₀ -alkylene, B can be a straight-chain or branched chain alkylenegroup, for example methylene, di-, tri-, tetra-, hexa-, octa-,decamethylene, 1,3,3-trimethylbutylene-1,4, pentylene-3,3 or2-ethylpropylene-1,3.

As alkyl or substituted alkyl, R¹ and R² can be for example: methyl,ethyl, propyl, butyl, isopentyl, hexyl, isooctyl, hydroxymethyl,methoxymethyl, 2-cyanoethyl, 2-methoxycarbonylethyl,2-butoxycarbonylethyl, dimethylaminomethyl or 3-aminopropyl. When R¹ andR² together are alkylene, oxaalkylene or azaalkylene, they form,together with the C atom to which they are attached, for example acyclopentane, cyclohexane, cyclooctane, tetrahydropyrane, pyrrolidine orpiperidine ring. R¹ and R² are preferably C₁ -C₄ -alkyl, especiallymethyl, or R¹ and R² together are C_(2-C) ₈ -alkylene, particularlypentamethylene.

As alkylene, R³ can be a straight-chain or branched-chain alkyleneradical, for example methylene, ethylene, tri, tetra-, penta- orhexamethylene, 2,2-dimethylpropylene-1,3 or 2,3-dimethylbutylene-1,4. Asoxaalkylene, R³ can be for example 2-oxapropylene-1,3 or3-oxapentylene-1,5.

R⁴, R⁵, R⁶, R⁷ and R⁸ can be C₁ -C₄ -alkyl, for example: methyl, ethyl,isopropyl, n-butyl or sec-butyl. These radicals can also be C₃ -C₁₂-alkenyl, especially alkenylmethyl, for example allyl, methallyl or11-undecenyl. Furthermore, these radicals can be C₅ -C₆ -cycloalkyl,such as cyclopentyl or cyclohexyl.

R¹⁰ can be for example: methyl, ethyl, propyl, butyl, vinyl, propenyl,butenyl or phenyl.

As C₁ -C₁₂ -alkyl, R¹³ can be one of the alkyl groups given for R⁹. AsC₁ -C₄ -hydroxyalkyl, R¹³ and R¹⁴ can be for example hydroxymethyl,2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl.

As C₁ -C₄ -alkyl, R¹⁵ and R¹⁶ are in particular methyl; R¹⁷ as C_(1-C)₁₈ -alkyl can be for example: methyl, propyl, tert-butyl, 2-ethylhexyl,n-dodecyl or n-octadecyl. As C₇ -C₂₀ -alkylphenyl, R¹⁷ can be forexample: tolyl, butylphenyl, octylphenyl, nonylphenyl or dodecylphenyl.R¹⁷ can also be a technical mixture of various alkyl or alkylphenylradicals.

Preferred photoinitiators are compounds of the formula I, II or III inwhich Ar is a radical of the formula IV wherein at least one of theradicals R⁴ to R⁸ is a group --OH-- or --OR⁹. This group is preferablyinthe 4-position. The remaining positions of the phenyl radical can beunsubstituted or they can likewise carry a group --OR⁹ or some other ofthe substituents R⁴ to R⁸ defined above. R⁹ corresponds to thedefinition given in the foregoing.

Further preferred photoinitiators are in particular compounds of theformula I in which Ar is a phenyl radical which is substituted by 1 or 2of the groups --OH or OR⁹, R⁹ is C₁ -C₁₂ -alkyl, C₃ -C₆ -alkenyl,cyclohexyl, C₇ -C₉ -phenylalkyl, phenyl, phenyl substituted by C₁ -C₄-alkyl, or is tetrahydropyranyl or one of the groups --CH₂ CH₂ OH, --CH₂CH₂ --OOC--CH═CH₂, --CH₂ CN, --CH₂ COOH, --CH₂ COO(C₁ -C₈ -alkyl), --CH₂CH₂ CN, --CH₂ CH₂ COO(C₁ -C₈ -alkyl), --(CH₂ CH₂ O)_(q) --H,--Si(R¹⁵)(R¹⁶)₂, ##STR9## in which q is 2 to 10 and r is 2 to 8,

R¹ and R² independently of one another are each C₁ -C₄ -alkyl, phenyl orC₇ -C₉ -phenylalkyl, or R¹ and R² together are C₂ -C₈ -alkylene, and

X and X' are identical and are an amino group --N(R¹¹)(R¹²) wherein R¹¹is C₁ -C₈ -alkyl, C₂ -C₄ -alkyl substituted by OH, C₁ -C₄ -alkoxy or CN,or is C₃ -C₅ -alkenyl, and R¹² has one of the meanings given for R¹¹, ortogether with R¹¹ is C₄ -C₆ -alkylene which can be interrupted by --O--,--S-- or N(R¹⁴)--, wherein R¹⁴ is C₁ -C₄ -alkyl, 2-cyanoethyl,2-hydroxyethyl or 2-hydroxypropyl.

Particularly preferred photoinitiators are compounds of the formula I

wherein

Ar is a phenyl radical substituted in the 4-position by a group --OR⁹,

R⁹ is C₁ -C₈ -alkyl, C₃ -C₆ -alkenyl, cyclohexyl, benzyl, phenyl, tolylor one of the groups: --CH₂ CH₂ OH, --CH₂ CH₂ --OOC--CH═CH₂, --CH₂--COO(C₁ -C₄ -alkyl), --CH₂ CH₂ --COO(C₁ -C₄ -alkyl), ##STR10## R¹ andR² are C₁ -C₄ -alkyl, or R¹ and R² together are C₄ -C₅ -alkylene, and

X and X' are a morpholino radical or a radical of the formula --N(CH₂CH₂ OCH₃)₂.

Examples of photoinitiators of the formula I which can be used accordingto the present invention are the following compounds:

1-(4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

2-methyl-1-(4-phenoxyphenyl)-2-morpholinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-piperidinopropanone-1,

2-methyl-1-(4-phenoxyphenyl)-2-piperidinopropanone-1,

1-(4-ethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-isopropoxyphenyl)-2-methyl-2-morpholino-propanone-1,

1-(4-butoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-octyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-dodecyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-acetoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-isobutyryloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-acrylyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-benzoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-ethoxycarbonyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-methoxycarbonyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-N-ethylcarbamoyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-N,N-dimethylcarbamoyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-N,N-diethylcarbamoyloxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-[4-(2-tetrahydropyranyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-tetrahydrofuranyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-trimethylsilyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(triethylsilyloxy)phenyl]-2-methyl-2-morpholinobutanone-1,

1-[4-(tert.-butyldimethylsilyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[3-(dimethylphenyl-silyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(diphenyl-tert.-butylsilyloxy)phenyl]-2-ethyl-2-morpholinobutanone-1,

1-[4-(diphenylmethylsilyloxy)phenyl]-2-ethyl-2-morpholinohexanone-1,

1-[4-(methylsulfonyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(dodecylsulfonyloxy)phenyl-2-methyl-2-morpholinopropanone-1,

1-[4-(octadecylsulfonyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[3-(phenylsulfonyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(p-tolylsulfonyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(p-dodecylphenylsulfonyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(allyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-butenyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-(4-cyclohexyloxyphenyl)-2-methyl-2-morpholino-propanone-1,

1-[4-(2-hydroxycyclohexyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2,3-dihydroxypropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2,3-epoxypropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[3-(8-hydroxy-3,6-dioxaoctyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(53-hydroxy-3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51-heptadecaoxatripentacontyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(benzyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-hydroxy-2-phenyl-ethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-methoxyethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[3(2-butoxyethoxy)phenyl]-2-methyl-2-morpholino-propanone-1,

1-[2-[3-chloropropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(4-bromobutyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-cyanoethoxy)phenyl]-2-methyl-2-morpholino-propanone-1,

1-[4-(3-dimethylaminopropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-morpholinoethoxy)phenyl]-2-ethyl-2-morpholinohexanone-1,

1-[4-(2-ethoxycarbonylethoxy)phenyl]-2-ethyl-2-morpholinobutanone-1,

1-[4-(2-acryloyloxyethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(carboxymethoxy)phenyl]-2-methyl-2-morpholino-pentanone-1,

1-[4-(2-ethylhexyloxycarbonylmethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(3-morpholino-3-oxopropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-oxopropyloxy)phenyl-2-methyl-2-morpholinopropanone-1,

2-methyl-1-(4-tolyloxyphenyl)-2-morpholinopropanone-1,

2-methyl-1-[4-(phenethyloxy)phenyl]-2-morpholinopropanone-1,

1-[4-(4-chlorophenoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-carbethoxyphenoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-(2-methyl-4-phenoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-[3-isopropyl-4-(4-isopropylphenoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(3-dimethylamino-2-hydroxypropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[3-(2-(2-cyanoethoxy)ethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(3-mercaptopropyloxy)-3-methylphenyl]-2-methyl-2-morpholinopropanone-1

1-(4-anisoyl)-1-morpholinocyclohexane,

1-(4-ethoxybenzoyl)-morpholinocyclohexane,

1-(3-cyclohexyl-4-methoxybenzoyl)-1-morpholinocyclohexane,

1-(2-allyl-4,5-dimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-[4-(2-chloro-3-methoxyphenoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2,4-dibromophenoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

bis[4-(α-morpholinoisobutyroyl)phenoxy]-methane,

1,2-bis[4-(α-morpholinoisobutyroyl)phenoxy]-ethane,

1,4-bis[4-(α-morpholinoisobutyroyl)phenoxy]-butane,

1,3-bis[4-(α-morpholinoisobutyroyl)phenoxy]-2-hydroxy-propane,

4,4'-bis(α-morpholinoisobutyroyl)-diphenyl oxide,

1,4-di-[4-(α-morpholinoisobutyroyl)-phenoxy]-benzene,

di-[4-(α-morpholinoisobutyroyl)-phenyl]-adipate,

di-[4-(α-morpholinoisobutyroyl)-phenyl]-2,2,4-trimethylhexane-1,6-dioate,

di-[4-(α-morpholinoisobutyroyl)-phenyl]-nonane-1,9-dioate,

di-[4-(α-morpholinoisobutyroyl)-phenyl]-oxalate,

dimethyl-di[4-(α-morpholinoisobutyroyl)-phenyl]-silane,

1,3-di[4-(α-morpholinoisobutyroyl)-phenyl]-1,1,3,3-tetramethyldisiloxane,

1-(4-methoxyphenyl)-2-methyl-2-pyrrolidinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-oxazolidinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-piperazinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(4-methylpiperazino)propanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(2-methoxyethyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(2,6-dimethylmorpholino)propanone-1,

1-(4-methoxyphenyl)-2-methyl-2[4-(2-hydroxypropyl)piperazino[propanone-1,

1-(4-(methoxyphenyl)-2-methyl-2-[4-(2-hydroxyethyl)piperazino]propanone-1,

1-(4-methoxyphenyl)-2-methyl-2-dimethylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-diethylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-dibutylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(N-methylanilino)-propanone-1,

1-(4-methoxyphenyl)-2-methyl-2-butylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-ethylhexyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(4-ethoxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(3,4-dimethoxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(4-hydroxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-ethoxyethyl)aminopropanone-1,

1-(4-methoxybenzoyl)-1-di(2-methoxyethyl)aminocyclohexane,

1-(3,4-dimethoxybenzoyl)-1-di(2-methoxyethyl)aminocyclohexane,

1-(4-methoxyphenyl)-2-methyl-2-di(2-hydroxyethyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-cyclohexylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-N-methylcyclohexylaminobutanone-1,

1-(4-ethoxyphenyl)-2-methyl-2-dodecylaminopropanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-dibenzylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-dialhylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-methyl-2-(2-hydroxyethyl)aminopropanone-1,

1-(4-phenoxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(4-phenoxyphenyl)-2-methyl-2-(4-methylpiperazino)-propanone-1,

1-(4-hydroxybenzoyl)-1-morpholinocyclohexane,

1-(4-methoxyphenyl)-2-methyl-2-amino-propanone-1,

1-(3,4-dimethoxyphenyl)-2-methyl-2-isopropylaminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-methylaminopropanone-1,

1-(4-methoxybenzoyl)-1-metylaminocyclopentane,

1-(4-methoxybenzoyl)-1-morpholinocyclopentane,

1-(4-methoxyphenyl)-2-methyl-2-(N-methyl-2-hydroxyethylamino)propanone-1,

1-(4-ethoxyphenyl)-2-ethyl-2-di(2-cyanoethyl)aminobutanone-1,

1-(4-isopropoxyphenyl)-2-methyl-2-di(2-carbethoxyethyl)aminobutanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-(4-carbethoxyphenyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(2-methoxy-1-methylethylamino)propanone-1,

1-(4-methoxyphenyl)-2-methyl-2-[N-(2-hydroxypropyl)-2-methoxy-1-methylethylamino]-propanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(N-methyl-4-carbomethoxyphenylamino)propanone-1,

1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-2-(3-chloro-4-ethylphenyl)-aminopropanone-1,

1(4-methoxyphenyl)-2-methyl-2-(2,5-dichloro-phenyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-thiomorpholinopropanone-1,

1-(4-methoxphenyl)-2-methyl-2-[4-(2-carbethoxyethyl)piperazino]propanone-1,

2-(4-anisoyl)-2-methyl-pyrrolidine,

2-(4-anisoyl)-1-(2-hydroxyethyl)-2-methyl-pyrrolidine,

3,4-dimethyl-4-(3-propoxybenzoyl)oxazolidine,

1,2-dimethyl-2-(4-anisoyl)-piperidine,

3-(4-anisoyl)-3-methyl-1,2,3,4-tetrahydroisoquinoline,

3-(4-anisoyl)-3-benzyl-1,2,3,4-tetrahydroisoquinoline,

3-(3,4-dimethoxybenzoyl)-3-methyl-1,2,3,4-tetrahydroisoquinoline,

3-(4-anisoyl)-2,3-dimethyl-1,2,3,4-tetrahydroisoquinoline,

3-(3-propoxybenzoyl)-3-methyl-2-allyl-1,2,3,4-tetrahydroisoquinoline,

3-(4-ethoxybenzoyl)-3-methyl-2-(2-hydroxyethyl)-1,2,3,4-tetrahydroisoquinoline,

3-(3,4-dimethoxybenzoyl)-3-methyl-2-(2-hydroxyethyl)-1,2,3,4-tetrahydroisoquinoline,

3-(3,4-methylenedioxybenzoyl)-2,3-dimethyl-1,2,3,4-tetrahydroisoquinoline,

1-[4(cyanomethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(methallyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-(N-methyl-2-hydroxypropylamino)propanone-1,

2-(4-anisoyl)-1,2-dimethyl-4-phenylpyrrolidine,

1-(4-methoxyphenyl)-2-methyl-2-morpholinobutanone-1,

1-(4-methoxyphenyl)-2-methyl-2-morpholinopentanone-1,

1-(4-methoxyphenyl)-2-ethyl-2-morpholinobutanone-1,

1-(4-methoxyphenyl)-2-ethyl-2-morpholinohexanone-1,

1-(4-methoxyphenyl)-2-propyl-2-morpholinopentanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminobutanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopentanone-1,

1-(4-methoxyphenyl)-2-ethyl-2-di(2-methoxyethyl)aminobutanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-morpholinobutanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-morpholinopentanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-ethyl-2-morpholinohexanone-1,

1-(4-hydroxyphenyl)-2-methyl-2-morpholinobutanone-1,

1-(4-hydroxyphenyl)-2-ethyl-2-morpholinobutanone-1,

1-(4-hydroxyphenyl)-2-propyl-2-morpholinopentanone-1,

1-(4-hydroxyphenyl)-2-ethyl-2-morpholinohexanone-1,

1-(4-hydroxybenzoyl)-1-morpholinocyclopentane,

1-[4-(2-hydroxyethoxy)benzoyl]-1-morpholinocyclohexane,

1-(4-methoxybenzoyl)-1-dimethylaminocyclohexane,

1-(4-methoxybenzoyl)-1-morpholinocyclopropane,

3-(4-methoxybenzoyl)-3-morpholinotetrahydropyrane,

4-(4-ethoxybenzoyl)-3,4-dimethyloxazolidine,

2-(4-ethoxybenzoyl)-1,2-dimethylpiperidine,

1-(4-methoxyphenyl)-2-morpholino-2-phenyl-propanone-1,

1-(4-methoxyphenyl)-2-diethylamino-2-phenyl-propanone-1,

1,2-bis(4-methoxyphenyl)-2-morpholinopropanone-1,

1-[4(2-hydroxyethoxy)phenyl]-2,2-diphenyl-2-morpholinoethanone-1,

1-(4-methoxyphenyl)-2-methyl-2,3-dimorpholinopropanone-1,

1-(3-methoxyphenyl)-3-methoxy-2-methyl-2-morpholinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-morpholino-4-carbethoxybutanone-1,

1-(4-ethoxyphenyl)-2-methyl-2-morpholino-4-cyanobutanone-1,

1-[3-(2-hydroxyethoxy)phenyl]-2-methyl-2-morpholino-5-di(2-hydroxyethyl)aminopentanone-1,

1-(4-methoxyphenyl)-2-methyl-2-morpholinopenten-4-one-1,

1-(4-methoxyphenyl)-2-methyl-2-morpholino-3-phenylpropanone-1,

1-(4-methoxyphenyl)-2-benzyl-2-morpholino-3-phenylpropanone-1,

1-(2,3-dihydro-1,4-benzodioxin-6-yl)-2-methylmorpholinopropanone-1,

1-(2,3-dihydro-1,4-benzodioxin-6-yl)-2-methyl-2-di(methoxyethyl)aminopropanone-1,

1-(2,3-dihydro-1,4-benzodioxin-6-yl)-2-methyl-2-(4-methylpiperazino)pentanone-1,

1-(2,3-dihydro-1,4-benzodioxin-6-yl)-2-methyl-2-piperidinopropanone-1,

1-(1,3-benzodioxol-5-yl)-2-methyl-2-piperidinopropanone-1,

1-(1,3-benzodioxol-5-yl)-2-methyl-2-morpholinopropanone-1,

1-(1,3-benzodioxol-5-yl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(1,3-benzodioxol-5-yl)-2-methyl-2-pyrrolidinopropanone-1,

1-(1,3-benzodioxol-5-yl)-2-methyl-2-pyrrolidinobutanone-1,

1-(1,3-benzodioxol-5-yl)-2-methyl-2-pyrrolidinopentanone-1,

1-(3,4-dihydro-2H-1,5-benzodioxepin-7-yl)-2-methyl-2-morpholinopropanone-1,

1-(2,3-dihydrobenzofuran-5-yl)-2-methyl-2-morpholinopropanone-1,

1-(2,3-dihydrobenzofuran-5-yl)-2-methyl-b2-di(2-methoxyethyl)aminopropanone-1,

1-(2,3-dihydro-2-methyl-benzofuran-5-yl)-2-methyl-2-morpholinopropanone-1,

1-(2,3-dihydro-2-methylbenzofuran-5-yl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(chroman-6-yl)-2-methyl-2-morpholinopropanone-1,

1-(dibenzofuran-2-yl)-2-methyl-2-morpholinopropanone-1,

1-(dibenzofuran-2-yl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(dibenzofuran-2-yl)-2-methyl-2-piperidinopropanone-1,

1-(dibenzofuran-2-yl)-2-ethyl-2-morpholinohexanone-1,

1-(9H-xanthen-3-yl)-2-methyl-2morpholinopropanone-1,

1-(9H-xanthen-3-yl)-2-methyl-2-di(2-ethoxyethyl)aminopropanone-1,

1-(dibenzo[b,e][1,4]dioxin-2-yl)-2-methyl-2-morpholinopropanone-1,

1-(dibenzo[b,e][1,4]dioxin-2-yl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(10,11-dihydro-dibenz[b,f]oxepin-2-yl)-2-methyl-2-morpholinopropanone-1,

2,8-bis(α-morpholinoisobutyroyl)-dibenzofuran,

2,8-bis[α-di(2-methoxyethyl)aminoisobutyroyl]-dibenzofuran,

2-(α-morpholino-isobutyroyl)-8-[α-(di-(2-methoxyethyl)amino)isobutyroyl]-dibenzofuran,

3,6-bis(α-morpholinoisobutyroyl)-9H-xanthene,

2,8-bis(α-morpholinoisobutyroyl)-dibenzo[b,e][1,4]dioxine,

2,8-bis(α-morpholinoisobutyroyl)-10,11-dihydrodibenz[b,f]oxepine,

1-(2-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3,4-dimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4,5-dimethoxy-2-bromophenyl)-2-methyl-2-morpholinopropanone-1,

1-(4,5-dimethoxy-3-bromophenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,4,6-trimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3,4,5-trimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,4-dimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,4,5-trimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,3,4-trimethoxy-6-methylphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,5-dimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,5-dimethoxy-3-bromophenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,5-diethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,5-diethoxy-3-chlorophenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-hydroxy-3-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(4-acetoxy-3-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-[4-(trimethylsilyloxy)-3-methoxyphenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(1-ethoxyethoxy)-3-methoxyphenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-tetrahydropyranyloxy)-3-methoxyphenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-hydroxyethoxy)-3-methoxyphenyl]-2-methyl-2-morpholinopropanone-1,

1-(2-methoxy-5-methylphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2-allyl-4,5-dimethoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-[2-methoxy-5-(prop-1-enyl)-phenyl]-2-methyl-2-morpholinopropanone-1,

1-(2,3-dichloro-4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3-fluoro-4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(5-bromo-2-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(5-chloro-2-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-[4-(2-bromoethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(3-bromopropoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-morpholinoethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2,3-epoxypropyloxy)phenyl]-2-methyl-2-piperidinopropanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-di(2-methoxyethyl)aminopropanone-1

1-(4-phenethyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(2-methyl-4-phenoxyphenyl)-2-methyl-2-piperidinopropanone-1,

2-methyl-4,4'-bis(α-morpholinoisobutyroyl)-diphenyl oxide,

4-(α-morpholinoisobutyroyl)-4'-[α-di(2-methoxyethyl)aminoisobutyroyl]-diphenyloxide,

1-(4-hydroxyphenyl)-2-methyl-2-di(2-methoxyethyl)aminopropanone-1,

1-(3,5-dimethyl-4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3-tert.-butyl-4-hydroxy-5-methyl-phenyl)-2-methyl-2-morpholinopropanone-1,

1-(3,5-di-tert.-butyl-4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3-carbethoxy-4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3-carbethoxy-4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(3,4-dihydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,4-dihydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,5-dihydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,3,4-trihydroxyphenyl)-2-methyl-2-morpholinopropanone-1,

1-(2,3,4,5,6-pentamethoxy-phenyl)-2-methyl-2-morpholinopropanone-1,

1-[4-(2-hydroxyethoxy)phenyl]-2-amino-2-methylpropanone-1,

1-[3,4,5-tris-(2-hydroxyethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-ethoxypropyloxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-methoxypropyl)aminopropanone-1,

1-(4-hydroxyphenyl)-2-methyl-2-di(2-hydroxypropyl)aminopropanone-1,

1-(4-methoxyphenyl)-2-methyl-2-di(2-butoxyethyl)aminopropanone-1,

7a(7H)-(4-anisoyl)-1H,3H,5H-oxazolo[3,4-c]oxazole,

1-[4-(2-acryloyloxyethoxy)phenyl]-2-methyl-2-morpholinopropanone-1,

1-[4-(2-propionyloxyethoxy)phenyl]-2-methyl-2-morpholinobutanone-1.

The following compounds are examples of photoinitiators of the formulaII:

1,4-bis(4-methoxyphenyl)-2,3-dimethyl-2,3-dimorpholino-1,4-butanedione,

1,5-bis(4-methoxyphenyl)-2,4-dimethyl-2,4-dimorpholino-1,5-pentanedione,

1,6-bis[4-(2-hydroxypropyloxy)phenyl]-2,5-dimethyl-2,5-dimorpholino-1,6-hexanedione,

1,10-bis(4-phenethyl)-2,9-dibenzyl-2,9-dimorpholino-1,10-decanedione,

1,7-bis[3-(2-hydroxyethoxy)phenyl]-2,6-dimethyl-2,6-dimorpholino-4-oxa-1,7-pentanedione,

1,9-bis(3,4-methylenedioxyphenyl)-2,8-dimethyl-2,8-bis(N-methyl-2-methoxyethylamino)-5-oxa-1,9-nonanedione,

α,α'-bis(4-hydroxybenzoyl)-α,α'-bis-piperidino-1,4-diethylcyclohexane,

1,4-bis(4-anisoyl)-1,4-dimorpholinocyclohexane,

1,2-bis(4-anisoyl)-1,4-dimorpholinocyclohexene-4,

1-[4-(2-carbethoxyethoxy)benzoyl]-3-diethylamino-3-(4-hydroxybenzoyl)-1-morpholinocyclopentane,

2,3-bis-[4-(2-hydroxyethoxy)benzoyl]-2,3-bis(dimethylaminobicyclo[2.2.1]heptane,

2,3-bis(4-anisoyl)-2,3-dimorpholinobicyclo[2.2.1]heptene-5.

The following compounds are examples of photoinitiators of the formulaIII:

2,2'-(1,4-piperazinediyl)bis[1-(4-(2-hydroxyethoxy)phenyl-2-methylpropanone-1],

2,2'-(1,4-piperazinediyl)bis[1-(4-methoxyphenyl)-2-methylbutanone-1],

2,2'-(methylimino)bis[1-(4-methoxyphenyl)-2-methylpropanone-1],

2,2'-(benzylimino)bis[2-methyl-1-(4-phenethyl)-propanone-1],

2,2'-(2-hydroxyethylimino)bis[2-methyl-1(3,4-methylenedioxyphenyl)butanone-1],

1,8-bis-(3-methoxyphenyl)-3-(N)-ethyl-2,2,7,7-tetramethyl-3,6-diaza-1,8-octanedione,

1-[4-(2-hydroxyethoxy)phenyl]-12-(4-hydroxyphenyl)-3,10-bis(2-hydroxyethyl)-2,2,11,11-tetramethyl-3,10-diaza-1,12-dodecanedione,

N,N'-bis[1-(4-anisoyl)cyclohexyl]-N,N'-dimethyl-1,3-diaminopropane.

Some of the compounds of the formulae I, II and III are known compounds,the genral preparation of which is described in European PatentApplication Publication No. 3002. Others are novel compounds whichlikewise form subject matter of the present invention. These arecompounds of the formulae I, II and III in which Ar is anoxygen-containing aromatic radical, selected from the followingformulae: ##STR11## wherein Z is a direct bond, --CH₂, --CH₂ CH₂ -- or--O--,

Z' is --CH₂ CH₂ -- or --(CH₂)₃ --, each unsubstituted or substituted byCH₃,

R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one another are hydrogen,halogen, C₁ -C₄ -alkyl, C₃ -C₁₂ -alkenyl, C₅ -C₆ -cycloalkyl, phenyl,--COOH, --COO(C₁ -C₄ -alkyl), --OH or --OR⁹, with the proviso howeverthat at least one of the radicals R⁴ to R⁸ is a group --OH or --OR⁹,

R⁹ is C₁ -C₁₂ -alkyl, C₃ -C₁₂ -alkenyl, cyclohexyl, hydroxycyclohexyl,C₁ -C₄ -alkyl which is substituted by one or more of the groups Cl, Br,CN, SH, --N(C₁ -C₄ -alkyl)₂, piperidino, morpholino, OH, --O(C₁ -C₄-alkyl), --OCH₂ CH₂ CN, --OCH₂ CH₂ COO(C₁ -C₄ -alkyl), --OOC--R¹⁰,--COOH, --COO(C₁ -C₈ -alkyl), --CONH(C₁ -C₄ -alkyl), --CON(C₁ -C₄-alkyl)₂, ##STR12## --CO--(C₁ -C₄ -alkyl) or --CO--phenyl, or is2,3-epoxypropyl, --(CH₂ CH₂ O)_(q) --H, phenyl, C₇ -C₉ -phenylalkyl, C₇-C₉ -phenylhydroxyalkyl, phenyl which is substituted by halogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy or --COO(C₁ -C₄ -alkyl), or is tetrahydropyranyl,tetrahydrofuranyl, a group --CO--R¹⁰, --COO(C₁ -C₈ -alkyl), --CONH(C₁-C₄ -alkyl), --CON(C₁ -C₄ -alkyl), --CON(C₁ -C₄ -alkyl)₂,--Si(R¹⁵)(R¹⁶)₂, --SO₂ --R¹⁷ or a radical of the formula ##STR13##wherein p is 1 to 4, q is 2 to 20, A is oxygen or sulfur, and B is adirect bond or a C₁ -C₁₀ -alkylene radical, or R⁹ is a radical of theformula ##STR14## R¹⁰ is C₁ -C₄ -alkyl, C₂ -C₄ -alkenyl or phenyl, X andX' are an amino group --N(R¹¹)(R¹²),

Y is a divalent radical of the formula ##STR15## --N(R¹³)-- or--N(R¹³)--(CH₂)_(x) --N(R^(13'))--, wherein x is 1 to 8,

R¹¹ is C₁ -C₁₂ -alkyl, C₂ -C₄ -alkyl which is substituted by one or moreof the groups OH, C₁ -C₄ -alkoxy, CN or --COO(C₁ -C₄ -alkyl), or is C₃-C₅ -alkenyl, cyclohexyl, C₇ -C₉ -phenylalkyl, phenyl or phenylsubstituted by Cl, C₁ -C₄ -alkyl, OH, C₁ -C₄ -alkoxy or --COO(C₁ -C₄-alkyl), or R¹¹ and R¹ together are the group --CH₂ OCH₂ --,

R¹² has one of the meanings given for R¹¹ or together with R¹¹ is C₅ -C⁷-alkylene, or C₃ -C⁷ -alkylene which is interrupted by --O--, --S-- or--N(R¹⁴), or R¹² together with R² is C₁ -C₈ -alkylene, C₇ -C₁₀-phenylalkylene or C₂ -C₄ -oxaalkylene or azaalkylene,

R¹³ and R^(13') are hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₄ -hydroxyalkyl,cyclohexyl or benzyl,

R¹⁴ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -hydroxyalkyl, --CH₂ CH₂ CN or--CH₂ CH₂ COO(C₁ -C₄ -alkyl),

R¹⁵ and R¹⁶ are C₁ -C₄ -alkyl or phenyl,

R¹⁷ is C₁ -C₁₈ -alkyl, phenyl or C₇ -C₂₀ -alkylphenyl,

Ar' has one of the meanings given for Ar,

R¹ and R² independently of one another are each C₁ -C₈ -alkyl, C₁ -C₄-alkyl which is substituted by OH, C₁ -C₄ -alkoxy, CN, --COO(C₁ -C₈-alkyl) or --N(R¹¹)(R¹²), or are allyl, phenyl, chlorophenyl, R⁹--O--phenyl or C₇ -C₉ -phenylalkyl, or R¹ and R² together are C₂ -C₈-alkylene, C₃ -C₉ -oxaalkylene or azaalkylene,

R³ is a direct bond, C₁ -C₆ -alkylene, C₂ -C₆ -oxaalkylene orcyclohexylene, or together with the two substituents R² and the two Catoms to which these substituents are attached forms a cyclopentane,cyclohexane, cyclohexene, endomethylenecyclohexane orendomethylenecyclohexene ring,

and the acid addition salts of these compounds, with the reservationthat, in the case of compounds of the formula I in which R¹ and R² aremethyl and Ar is 4-methoxyphenyl or 4-phenoxyphenyl, X is not apiperidino radical.

Preferred compounds amongst these are those of the formula I in which Aris a phenyl radical substituted in the 4-position by a group --OR⁹.Particularly preferred are the compounds of the formula I in which Ar isa phenyl radical substituted in the 4-position by the group --OR⁹, R⁹ isC₁ -C₈ -alkyl, C₃ -C₆ -alkenyl, cyclohexyl, benzyl, phenyl, tolyl or oneof the groups, --CH₂ CH₂ OH, --CH₂ CH₂ --OOC--CH═CH₂, --CH₂ --COO(C₁ -C₄-alkyl), --CH₂ CH₂ --COO(C₁ -C₄ -alkyl), ##STR16## R¹ and R² are C₁ -C₄-alkyl, or R¹ and R² together are C₄ -C₅ -alkylene, and X and X' are amorpholino radical or a radical of the formula --N(CH₂ CH₂ --OCH₃)₂.

The compounds of the formula I can be produced, using methods analogousto those known from the European Patent Application, Publication No.3002, by introduction of the amino group into a corresponding arylhaloalkyl ketone V in accordance with the following reaction stages:##STR17##

In these formulae Hal is halogen, in particular chlorine or bromine. Ifthere is used in the final reaction stage half a mole of a primary amineR¹³ NH₂, or piperazine or a di-secondary diamine R¹³ NH--(CH₂)_(x)--NHR¹³, there are obtained the corresponding compounds of the formulaIII.

The compounds of the formula II can be produced, in a manner analogousto that in which compounds of the formula I are obtained, by using, asstarting material, diketones of the general formula Va ##STR18##

The haloalkyl ketones V can be produced from the correspondingaryl-alkyl ketones Ar--CO--CH(R¹)(R²) by the customary methods ofα-halogenation of ketones. Alternatively, they can be obtained also fromthe aromatic compounds ArH by a Friedel-Crafts reaction with anα-halocarboxylic acid halide Hal--C(R¹)(R²)--COHal.

The dihalodiketones Va can be produced analogously by α-halogenation ofthe corresponding diketones, or by a Friedel-Crafts reaction with anα,α'dihalodicarboxylic acid halide.

In the production of compounds of the formula I, II or III in which Aris a phenyl radical substituted by the group --OH, by the methoddescribed in the foregoing, it is advisable to protect the phenolic OHgroup by a protecting group before halogenation, for example by an ethergroup, acyl group or sulfonyl group. This protecting group can then beremoved by hydrolysis after amination. The same applies for compoundshaving the --OR⁹ group, when there is a risk that R⁹ will react withhalogen. In this case, the phenol group is firstly protected by aprotecting group, the protecting group is removed after halogenation andamination and, as the final step, the radical R⁹ is introduced by thecustomary methods of etherification or esterification of phenolichydroxyl groups, preferably by reaction with the corresponding halide R⁹Hal.

When R⁹ is a radical --(CH₂ CH₂ O)_(q) --H, this is introduced byreaction with ethylene oxide. As tetrahydropyranyl or tetrahydrofuranylradical, R⁹ can be introduced by the acid-catalysed addition ofdihydropyrane or dihydrofuran to the phenolic OH group. In an analogousmanner, also vinyl ether, acrylonitrile and acrylic acid ester can beadded by an acid- or base-catalysed reaction, by which means there areobtained compounds in which R⁹ is an ethyl radical substituted byalkoxy, cyano or --COO(C₁ -C₈ -alkyl).

A further possibility for producing compounds of the formula I is thereaction of α-aminoalkyl nitriles with the corresponding aryllithiumcompounds: ##STR19##

Compounds of the formula II or III can be produced from thecorresponding dinitriles in an analogous manner.

Compounds of the formula I in which X is an --NH₂ or --NHR¹⁰ group can,alternatively, be produced in an intramolecular Houben-Hoesch reaction,from the corresponding benzylaminoacetonitriles, by cyclisation inconcentrated sulfuric acid to the imidazolines VI, according to D. N.Harcourt, N. Taylor, R. D. Waigh, J. Chem. Res. (S), 1978, 154; andsubsequent hydrolysis of VI by the method of M. R. Euerby and R. D.Waigh, J. Chem. Res. (S), 1982, 240: ##STR20##

The acid addition salts of the compounds I, II and III can be producedin the customary manner from the aminoketones by neutralisation with aprotonic acid. Examples of such acids are: HCl, HBr, H₃ PO₄, H₂ SO₄,toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid,hexadecanesulfonic acid, HBF₄ or HPF₆.

Further details regarding the synthesis of compounds of the formulae I,II and III can be learnt from the following production examples.

EXAMPLE A Production of aminoketones by way of the α-haloketones (A₁)4-Methoxy-isobutyrophenone

160 g (1.2 mols) of finely powdered aluminium chloride are placed into500 ml of tetrachloroethylene and cooled to 0°-5° C. To the whitesuspension is added dropwise a mixture of 108 g (1.0 mol) of anisole and117 g (1.1 mols) of isobutyric acid chloride. At unchanged temperature,the mixture is subsequently allowed to react for 3 hours with vigorousstirring, and the thickly liquid, yellowish suspension is then pouredinto ice-water. The organic phase is separated, dried over sodiumsulfate and concentrated in a rotary evaporator. The residue is purifiedby vacuum distillation to thus obtain 171 g (96% of theory) ofcolourless liquid having a boiling point of 84° C. at 3.4 mbar.

The NMR spectrum is compatible with the given structure.

NMR (CDCl₃), δ (ppm): 1.17 (d, 6H, J=7 Hz); 3.43 (m, 1H); 3.73 (s, 3H);6.77 and 7.77 (AA'BB' system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

(A₂) 4-Methoxy-α-bromoisobutyrophenone

178 g (1 mol) of 4-methoxyisobutyrophenone are placed into 300 ml ofchlorobenzene, and 160 mg (1 mol) of bromine are added dropwise at roomtemperature with stirring. After completion of the dropwise addition,the mixture is allowed to react for 3 hours, and residues of the formedHBr gas are subsequently expelled from the solution with a stream ofnitrogen. The solvent is then removed in a rotary evaporator at a bathtemperature of 40° C. There remain as residue 257 g (100% of theory) ofthe α-bromoketone in the form of yellowish-brown oil, which can be usedwithout further purification for the next reaction.

The NMR spectrum of the crude product is compatible with the givenstructure.

NMR (CDCl₃), δ (ppm): 1.99 (s, 6H); 3.72 (s, 3H); 6.71 and 8.01 (AA'BB'system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

(A₃) 2-Methoxy-2-(4-methoxyphenyl)-3,3-dimethyloxirane

A solution of 70 g (1.3 mols) of sodium methoxide in 170 g of methanolis taken at room temperature and, with vigorous stirring, 257 g (1 mol)of the crude bromoketone from A₂ are added dropwise. The temperature iskept at 20°-25° C. by slight cooling. After the dropwise addition hasbeen completed, stirring is continued for 2 hours; the formed whitesuspension is then diluted with 200 ml of toluene, and the sodiumbromide which has precipitated is filtered off. The filtrate isconcentrated in the rotary evaporator, in the course of which furthersodium bromide precipitates. After renewed filtration the crude productis purified by vacuum distillation. The yield is 180 g (86% of theory)of the epoxyether in the form of a colourless liquid which boils at 64°C./2.5 mbar, m.p. 41°-43° C. The NMR spectrum is compatible with thegiven structure.

NMR (CDCl₃), δ (ppm): 0.97 (s, 3H); 1.49 (s, 3H); 3.10 (s, 3H); 3.70 (s,3H); 6.73 and 7.19 (AA'BB' system, J_(AB) =8.5 Hz, J_(AB') ≦1 Hz, 4H).

(A₄) 1-(4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1

208 g (1 mol) of the epoxyether from A₃) are refluxed in 348 g (4 mols)of morpholine for 12 hours, the forming methanol being continuouslydistilled off. The cooled solution is concentrated in a rotaryevaporator, and the residue is recrystallised from hexane. There areobtained 237 g of the pure product as colourless crystals, m.p. 75°-76°C. The NMR spectrum is compatible with the given structure.

NMR (CDCl₃), δ (ppm): 1.28 (s, 6H); 2.52 (m, 4H); 3.61 (m, 4H); 3.77 (s,3H); 6.73 and 8.41 (AA'BB' system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

    ______________________________________                                        Elementary analysis:                                                                          C      H        N    O                                        ______________________________________                                        calculated:     68.42  8.04     5.32 18.23%                                   found:          68.19  8.06     5.33 18.25%                                   ______________________________________                                    

The aminoketones given in Table I are produced in an analogous manner.

                                      TABLE 1                                     __________________________________________________________________________    Compound                               Physical                                                                              Elementary analysis (%)        No.   Formula                          data °C.                                                                           C   H   N                  __________________________________________________________________________           ##STR21##                       m.p. 75-76°                                                                    cal. found                                                                        68.42 68.19                                                                        8.04 8.06                                                                         5.32 5.33         2                                                                                    ##STR22##                       b.p. 180°                                                                      cal. found                                                                        73.53 72.7                                                                         8.87 9.0                                                                          5.36 5.3          3                                                                                    ##STR23##                       m.p. 99-101°                                                                   cal. found                                                                        73.82 73.51                                                                        7.13 7.01                                                                         4.31 4.42         4                                                                                    ##STR24##                       b.p..sub.o,1 180°                                                              cal. found                                                                        77.99 77.7                                                                         7.80 7.7                                                                          4.33 3.5          5                                                                                    ##STR25##                       m.p. 140-141°                                                                  cal. found                                                                        74.28 74.3                                                                         6.55 6.6                                                                          4.33 4.4          6                                                                                    ##STR26##                       liquid  cal. found                                                                        65.99 65.93                                                                        8.80 8.76                                                                         4.53 4.48         7                                                                                    ##STR27##                       m.p. 62-64°                                                                    cal. found                                                                        69.53 69.24                                                                        8.75 8.70                                                                        10.14 10.16        8                                                                                    ##STR28##                       oil     cal. found                                                                        68.67 68.46                                                                        8.45 8.67                                                                        10.68 10.43        9                                                                                    ##STR29##                       m.p. 89-92°                                                                    cal. found                                                                        66.91 66.77                                                                        8.42 8.34                                                                         5.57 5.52         10                                                                                   ##STR30##                       oil     cal. found                                                                        74.71 74.71                                                                       10.23 10.27                                                                        4.61 4.61         11                                                                                   ##STR31##                       oil     cal. found                                                                        70.56 70.53                                                                        8.65 8.85                                                                         6.33 6.29         12                                                                                   ##STR32##                       liquid  cal. found                                                                        66.91 66.86                                                                        8.42 8.41                                                                         5.57 5.49         13                                                                                   ##STR33##                       liquid  cal. found                                                                        67.90 67.90                                                                        8.74 8.68                                                                         5.28 4.99         14                                                                                   ##STR34##                       viscous cal. found                                                                        70.07 69.83                                                                        8.65 8.54                                                                         4.81 4.72         15                                                                                   ##STR35##                       viscous cal. found                                                                        69.29 69.08                                                                        8.36 8.38                                                                         5.05 5.09         16                                                                                   ##STR36##                       m.p. 74-76°                                                                    cal. found                                                                        71.44 71.39                                                                        9.15 9.03                                                                         4.38 4.26         17                                                                                   ##STR37##                       m.p. 84-87°                                                                    cal. found                                                                        65.51 66.24                                                                        7.90 7.87                                                                         4.77 4.54         18                                                                                   ##STR38##                       viscous cal. found                                                                        65.51 65.51                                                                        7.90 7.85                                                                         4.77 4.79         18a                                                                                  ##STR39##                       m.p. 91-93°                                                                    cal. found                                                                        70.79 70.77                                                                        8.91 8.86                                                                         4.59 4.65         __________________________________________________________________________

(A₅) Chlorination with copper-II chloride1-(3,4-Dimethoxyphenyl-2-chloro-2-methylpropanone-1

79.1 g (0.38 mol) of 1-(3,4-dimethoxyphenyl)-2-methylpropanone-1,produced analogously to Example A₁, are dissolved in 400 ml of anisopropanol/water mixture 4:1, and 64.8 g (0.38 mol) of copper-IIchloride (dihydrate) are then added. The suspension is heated to thereflux temperature (about 80° C.), and the green solution becomesdarker. After 8 hours, a further 64.8 g (0.38 mol) of copper-II chlorideare added. The dark-green suspension is refluxed for a further 21 hours,and is afterwards cooled and filtered. The filtrate is diluted with 300ml of toluene, and the toluene solution is extracted three times with200 ml of water. The toluene solution is dried with sodium sulfate andconcentrated by evaporation. The crude product obtained is examined bymeans of gas-chromatography and NMR spectrum, and then furtherprocessed, in a manner analogous to that of Example A₃, to thecorresponding oxirane.

EXAMPLE B Production of the free phenol by ether cleavage1-(4,hydroxyphenyl-2-methyl-2-morpholinopropanone-1

131.7 g (0.5 mol) of1-(4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1 are dissolved in300 ml of hydrobromic acid (about 47%), and the solution is stirred at120° C. for 24 hours. It is subsequently cooled, and neutralised withconcentrated sodium hydroxide solution to pH 8.5. The formed suspensionis repeatedly extracted with diethyl ether. The ether is dried, andconcentrated by evaporation, and the crystals remaining behind arerecrystallised from a methanol/water mixture (5:1). The yield is 89 g ofcolourless crystals, m.p. 189°-192° C. (compound No. 19). The NMRspectrum is compatible with the given structure.

NMR (CDCl₃ /CH₃ OD), δ (ppm): 1.30 (s, 6H); 2.55 (m, 4H): 3.64 (m, 4H);4.32 (s, broad, 1H); 6.69 and 8.31 (AA'BB' system, J_(AB) =9 Hz, J_(AB')≦1 Hz, 4H).

    ______________________________________                                        Elementary analysis:                                                                          C          H      N                                           ______________________________________                                        calculated:     67.45      7.65   5.62                                        found:          67.47      7.67    5.61.                                      ______________________________________                                    

EXAMPLE C Silylation of the free phenol1-[4-(Trimethylsilyloxy)phenyl]-2-methyl-2-morpholinopropanone-1

To a suspension of 15.0 g (0.06 mol) of1-(4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1 in 50 ml of tolueneare added 3.6 g of hexamethyldisilazane and 0.2 g of4-dimethylaminopyridine. There are then added dropwise at roomtemperature 2.3 g of trimethylchlorosilane, and the suspension isstirred overnight. The ammonium chloride which has precipitated isfiltered off, and subsequently washed with toluene. The solution isconcentrated in a vacuum rotary evaporator. The yield is 18.0 g of alight-yellow oil which solidifies in the cold state in crystalline form,m.p. 59°-64° C. (compound No. 20). The NMR spectrum is compatible withthe given structure.

NMR (CDCl₃), δ (ppm): 0.32 (s, 9H); 1.29 (s, 6H); 2.50 (m, 4H); 3.60 (m,4H); 6.75 and 8.43 (AA'BB' system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

    ______________________________________                                        Elementary analysis                                                                          C          H      N                                            ______________________________________                                        calculated:    63.51      8.47   4.36%                                        found:         63.40      8.52    4.48%.                                      ______________________________________                                    

EXAMPLE D Etherification of the free phenol1-[4-(Allyloxy)phenyl]-2-methyl-2-morpholinopropanone-1

6.7 g (0.055 mol) of allyl bromide are added dropwise, at roomtemperature, to a suspension of 12.5 g (0.05 mol) of1-(4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1 and 7.6 g ofpowdered potassium carbonate in 30 ml of acetone. The mixture is heatedto 60° C. and stirred overnight at this temperature. The suspension isthen cooled, diluted with 100 ml of toluene and filtered. The solutionis concentrated in a vacuum rotary evaporator and diluted again with 100ml of toluene. The toluene solution is extracted with water, dried withpotassium carbonate and concentrated in a vacuum rotary evaporator.There are thus obtained 14 g of a yellow oil (compound No. 21). The NMRspectrum is compatible with the given structure.

NMR (CCl₄), δ (ppm): 1.21 (s, 6H); 2.42 (m, 4H); 3.50 (m, 4H); 4.35-4.58(m, 2H); 4.98-5.45 (m, 2H); 5.58-6.23 (m, 1H); 6.69 and 8.32 (AA'BB'system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

    ______________________________________                                        Elementary analysis:                                                                         C          H      N                                            ______________________________________                                        calculated:    70.56      8.01   4.84%                                        found:         70.56      8.09    4.83%.                                      ______________________________________                                    

EXAMPLE E Esterification of the free phenol1-(4-Acetoxyphenyl)-2-methyl-2-morpholinopropanone-1

12.5 g (0.05 mol) of1-(4-hydroxyphenyl)-2-methyl-2-morpholinopropanone-1, 6.2 g (0.06 mol)of acetic anhydride and 0.3 g (about 5 mol %) of dimethylaminopyridineare suspended in 50 ml of dioxane, and the suspension is stirred for twohours. There are then added dropwise 6.1 g (0.06 mol) of triethylamineand, after one hour's stirring, the formed solution is concentrated in avacuum rotary evaporator; the residue is subsequently dissolved in 100ml of toluene, and the solution is precipitated portionwise by theaddition of 300 ml of hexane. The crystals are filtered off, washed withhexane and dried. The result is 13.3 g of white crystals, m.p. 100°-103°C. (compound No. 22). The NMR spectrum is compatible with the givenstructure.

NMR (CCl₄), δ (ppm): 1.24 (s, 6H); 2.20 (s, 3H); 2.46 (m, 4H); 3.53 (m,4H); 6.94 and 8.38 (AA'BB' system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

EXAMPLE F N-Hydroxyalkylation1-(4-Methoxyphenyl)-2-methyl-2-[4-(2hydroxypropyl)piperazino]-propanone-1

8.9 g (0.034 mol) of1-(4-methoxyphenyl)-2-methyl-2-piperazinopropanone-1 are dissolved in 50ml of methanol, and the solution is cooled to 0° C. There is then added0.5 g of CO₂ as dry ice, and there are subsequently added dropwise 2.17g (0.037 mol) of propylene oxide. The solution is stirred for about 17hours at room temperature, and afterwards concentrated in the rotaryevaporator to leave 10.9 g of oil, which slowly solidifies into the formof a wax-like compound (compound No. 23). The structure ##STR40## isconfirmed by the NMR spectrum.

NMR (CCl₄), δ (ppm): 1.02 (d, 3H); 1.23 (s, 6H), 2.0-2.9 (m, 10H);3.2-3.9 (m, 2H); 3.75 (s, 3H); 6.69 and 8.32 (AA'BB' system, J_(AB) =9Hz, J_(AB') ≦1 Hz, 4H).

There is produced in an analogous manner from1-(4-methoxyphenyl)-2-methyl-2-(2-methoxyethyl)aminopropanone-1, withpropylene oxide,1-(4-methoxyphenyl)-2-methyl-2-[N-(2-hydroxypropyl)-N-(2-methoxyethyl)amino]propanone-1,which is obtained as liquid (compound No. 24). The structure ##STR41##is confirmed by the NMR spectrum.

NMR (CCl₄), δ (ppm): 0.9-1.2 (m, 3H); 1.33 (s, 6H); 2.4-2.6 (m, 6H);3.13 (s, 3H); 3.1-3.5 (m, 4H); 3.65 (s, 3H); 6.63 and 8.15 (AA'BB'system, J_(AB) =9 Hz, J_(AB') ≦1 Hz, 4H).

EXAMPLE G Salt formation 4-Dodecylbenzenesulfonate of1-(4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1

6.58 g (0.025 mol) of1-(4-methoxyphenyl)-2-methyl-2-morpholinopropanone-1 are dissolved in 20ml of absolute ether. There are then dissolved 8.16 g (0.025 mol) ofcommercial 4-dodecylbenzenesulfonic acid (Marlon®AS₃ acid, C. W. HulsAG) in 20 ml of ether, and the solution is added dropwise at roomtemperature, with cooling, to the amine. The white suspension whichprecipitates is filtered off and subsequently washed with 50 ml ofabsolute ether. The crystals are dried at 50° C., m.p. 118°-123° C.(compound (compound No. 25).

    ______________________________________                                        Elementary analysis: (589.83)                                                                  C       H      N     S                                       ______________________________________                                        calculated:      67.20   8.72   2.37  5.44%                                   found:           66.69   8.61   2.30   5.47%.                                 ______________________________________                                    

The pigmented compositions according to the invention contain anolefinically unsaturated, photopolymerisable binder. The binder canconsist of one or more unsaturated compounds; it contains preferably twoor three unsaturated compounds. In addition, the binder can containother film-forming components which are not unsaturated and do nottherefore participate in the polymerisation. The unsaturated compoundscan contain one or more olefinic double bonds. They can be of lowmolecular weight (monomeric) or of a higher molecular weight(oligomeric). Examples of monomers containing one double bond are alkylacrylates or methacrylates or hydroxyalkyl acrylates or methacrylates,for example methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethylacrylate, isobornyl acrylate or methyl or ethyl methacrylate. Furtherexamples of the monomers are acrylonitrile, acrylamide, methacrylamideN-substituted (meth)acrylamides, vinyl esters, such as vinyl acetate,vinyl ethers, such as isobutyl vinyl ether, styrene, alkylstyrenes,halogenostyrenes, N-vinylpyrrolidone, vinyl chloride or vinylidenechloride.

Examples of monomers containing several double bonds are ethylene glycoldiacrylate, propylene glycol diacrylate, neopentylglycol diacrylate,hexamethyleneglycol diacrylate or bisphenol A diacrylate,4,4'-bis-(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate or tetraacrylate, vinylacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallylphosphate, triallyl isocyanurate ortris-(2-acryloyloxyethyl)isocyanuate.

Examples of polyunsaturated compounds of higher molecular weight(oligomers) are acrylated epoxide resins, acrylated polyethers,acrylated polyurethanes or acrylated polyesters. Further examples ofunsaturated oligomers are unsaturated polyester resins, which in mostcases are prepared from maleic acid, phthalic acid and one or more diolsand which have molecular weights of about 500 to 3,000. Unsaturatedoligomers of this type can also be designated as prepolymers.

The binders for the photocurable compositions according to the inventioncan be, for example, a mixture of a monounsaturated and apolyunsaturated monomer.

In most cases, however, two-component mixtures of a prepolymercontaining a polyunsaturated monomer, or three-component mixtures whichalso contain, in addition, a monounsaturated monomer, are used. In thisrespect the prepolymer primarily determines the properties of thelacquer film; by varying it those skilled in the art can influence theproperties of the cured film. The polyunsaturated monomer functions as acrosslinking agent, which makes the lacquer film insoluble. Themonounsaturated monomer functions as a reactive diluent by means ofwhich the viscosity is reduced without the necessity of using a solvent.

Two-component and three-component systems of this type based on aprepolymer are used for printing inks as well as for lacquers,photoresists and other coloured, photocurable compositions.One-component systems based on photocurable prepolymers are alsofrequently used as binders for printing inks.

Unsaturated polyester resins are in most cases used in two-componentsystems together with a monounsaturated monomer, preferably styrene.Specific one-component systems, for example polymaleimides orpolychalcones, are often used for photoresists.

The binder can additionally contain non-photopolymerisable, film-formingcomponents. These can be, for example, polymers which dry physically orsolutions thereof in organic solvents, for example nitrocellulose orcellulose acetobutyrate. These can, however, also be chemically curableor heat-curable resins, for example polyisocyanates, polyepoxides ormelamine resins. The concomitant use of heat-curable resins is importantfor use in so-called hybrid systems, which are photopolymerised in afirst stage and are crosslinked in a second stage by subsequent heattreatment.

The photocurable compositions according to the invention contain apigment or a dye. They preferably contain a pigment. The pigment can bean inorganic pigment, for example titanium dioxide (rutile or anatase),iron yellow, iron red, chrome yellow, chrome green, nickel-titaniumyellow, ultramarine blue, cobalt blue, cadmium yellow, cadmium red orzinc white. The pigment can be an organic pigment, for example a monoazoor bisazo pigment or a metal complex thereof, a phthalocyanine pigmentor a polycyclic pigment, for example a perylene, thioindigo,flavanthrone, quinacridone, tetrachloroisoindolinone or triphenylmethanepigment. The pigment can also be a carbon black or a metal powder, forexample aluminium or copper powder. The pigment can also be a mixture oftwo or more different pigments, such as is customary for achievingspecific colour shades.

The pigment can be present in an amount of 5 to 60% by weight, based onthe total composition; 10-30% of pigment is present in most cases inprinting inks.

Dyes are frequently also used for imparting colour instead of pigmentsin photoresists or reprographic films. These can be organic dyesbelonging to a very wide variety of classes, for example azo dyes,methine dyes, anthraquinone dyes or metal complex dyes. In theconcentrations used, these dyes are soluble in the particular binders.The customary concentrations are 0.1 to 20%, preferably 1-5%, by weight,based on the total composition.

Problems similar to those in the radiation curing of colouredcompositions can also arise in the radiation curing of uncolouredcompositions containing a filler. In these cases too, thephotoinitiators described above can be used with success. Examples ofcompositions of this type are metal primers, priming coats and surfacefillers. Examples of fillers in compositions of this type are kaolin,talc, barytes, gypsum, chalk or silicate fillers.

In addition to the three essential components (binder, pigment andphotoinitiator), the photopolymerisable composition can contain furtherconstituents which depend especially on the intended field of use.Whereas solvent-free compositions are preferred for most purposes, itcan be necessary to add a solvent in order to achieve the viscosityrequired for the coating. The customary lacquer solvents, which arefrequently mixtures of different solvents, are suitable for thispurpose. Flow control auxiliaries, thixotropic agents or wetting agentscan also be added to achieve a uniform coating. Waxes or otherlubricants are frequently added in the case of printing inks. Thephotopolymerisable composition can also be in the form of an aqueousdispersion or solution.

Although the compositions according to the invention have an excellentstability to storage in the dark, it can be useful for certain purposes,for example for use in tropical countries, to add polymerisationinhibitors. Examples of inhibitors used for this purpose arehydroquinone and derivatives thereof, β-naphthols, sterically hinderedphenols, copper compounds, compounds of trivalent phosphorus,phenothiazine, quaternary ammonium compounds or hydroxylaminederivative.

Conversely, chain transfer agents, such as tertiary amines or thiolcompounds, can be added in order to accelerate UV curing or to achievespecific physical properties. The addition of free radical initiators,such as peroxides or other organic per-compounds and benzpinacol orother organic compounds which can be split by heat, can also acceleratephotopolymerisation in specific cases.

The compositions according to the invention can also contain aphotosensitiser which displaces the spectral sensitivity into specificranges. This can, for example, be an organic dye, perylene or aderivative of anthracene or thioxanthone. Thioxanthone derivatives, forexample alkylthioxanthones or thioxanthonecarboxylic acid esters, inparticular, effect a considerable acceleration of photopolymerisation,as sensitisers.

It is preferable to use only one compound of the formula I, II or III asa photoinitiator. However, in specific cases it can be advantageous touse a mixture of two such compounds or a mixture with another knownphotoinitiator. The quantity of photoinitiator required in thephotocurable coloured composition is 0.1-20% by weight, preferably 1-6%by weight.

The compositions according to the invention can be used for variouspurposes. The most important and preferred use is for printing inks.These can be printing inks for offset printing, letterpress printing,gravure printing, screen printing or flexographic printing. The printinginks according to the invention are particularly suitable for offsetprinting, screen printing and gravure printing.

A second important field of use is their use for paints. Pigmentedcoatings are used, in particular, as a primer for protecting metals fromcorrosion, but are also used as coloured top lacquers for decorativepurposes on all possible substrates, for example metal, wood, cardboard,plastics or textiles. The use of compositions according to the inventionfor white lacquers and for black-pigmented metal primers is ofparticular interest. Aqueous systems can also be used aselectrophoretically deposable lacquers.

Further fields of use are the radiation curing of photoresists, thephoto-crosslinking of silver-free films or other fields of photographicreproduction.

In all these uses the photocurable composition is applied in a thinlayer to a substrate. If a solvent was present, this is thensubstantially removed, for example by heating in a drying oven, bypassing warm air over the substrate or by infrared irradiation ormicrowave irradiation. The dried layer is then irradiated with shortwavelight, preferably with UV light within the wavelength range of 250-400nm. Examples of light sources suitable for this purpose aremedium-pressure, high-pressure and low-pressure mercury lamps and alsosuper-actinic fluorescent tubes. The radiation curing is preferablycarried out in a continuous process, the material to be cured beingconveyed past and beneath the source of radiation. The transport speedis decisive for the production rate of the article; it depends on theirradiation time required. For this reason, the acceleration ofradiation curing by photoinitiators is an important factor in theproduction of such articles, and it is one of the advantages of thephotoinitiators of the formulae I, II and III that they ensure rapidcuring even in a low concentration and even in the case of compositionshaving a high pigment content.

If a hybrid system is used as the binder, the curing of the film can becarried out in two stages. For example, a prepolymer is produced byradiation polymerisation of the photopolymerisable components, and thisis then completely cured by a thermal condensation reaction of thecomponents capable of undergoing condensation. A two-stage procedure ofthis type can be of interest, for example, for coating or bondingoperations, and also in curing relatively thick layers.

Another two-stage process is the combination of electron irradiation andUV irradiation, which is also of interest for fairly thick layers.Whereas the electron radiation effects curing in the depth of the film,the surface is cured by the UV irradiation.

The examples which follow illustrate the properties and applicability ofthe photocurable compositions according to the invention. In theseexamples the parts and percentages are by weight.

EXAMPLE 1

A blue printing ink is prepared in accordance with the followingformulation:

62 parts of Satalin®AP 565 (urethane acrylate resin made by Synthese,Holland),

15 parts of 4,4'-di-(β-acryloyloxyethoxy)-2,2-diphenylpropane(Ebecryl®150, UCB, Belgium) and

23 parts of Irgalithblau®GLSM (Ciba-Geigy AG, Basel).

The mixture is homogenised on a triple roll mill and ground to aparticle size of 5<μ.

5 g portions of this printing ink are mixed to form a homogenous mixturewith the desired quantity of photoinitiator on a disc grinding machineunder a pressure of 180 kg/m², while cooling with water.

Offset prints on strips of art printing paper measuring 4×20 cm are madewith this printing ink, using a test printing apparatus (made byPrufbaum, Federal Republic of Germany). The printing conditions are:

coating of printing ink: 1.5 g/m²

applied pressure: 25 kg/cm²

printing speed: 1 m/second

A printing roller with a metal surface (aluminium) is used.

The printed samples are irradiated in a UV irradiation apparatus (QCprocessor made by RPC, USA) with 2 lamps each with an output of 80watt/cm and a distance from the lamp of 11 cm. The irradiation time isvaried by varying the transport speed of the samples.

The surface drying of the printing ink is tested by the so-calledtransfer test immediately after irradiation. This is effected bypressing a white paper onto the printed sample under a pressure of 25kg/cm². If the paper remains colourless the test is successful. Ifvisible quantities of colour are transferred to the test strips, this isa sign that the surface of the sample is not yet adequately cured.

Table 2 shows the maximum transport speed at which the transfer test wasstill successful.

The completeness of cure of the printing ink is tested by againpreparing offset prints as described above, but using printing rollershaving a rubber surface and printing the metal side of aluminium-coatedpaper strips.

Irradiation is carried out as described above. Immediately afterirradiation, the completeness of the cure is tested in an REL apparatusfor testing complete curing. In this test, an aluminium cylinder coveredwith cloth is placed on the printed sample and rotated about its ownaxis once under a pressure of 220 g/cm² in the course of 10 seconds. Ifvisible damage takes place on the sample in the course of this, thecompleteness of the curing of the printing ink is inadequate. Table 2shows the maximum transport speed at which the REL test was stillsuccessful.

                  TABLE 2                                                         ______________________________________                                        Photoinitiator                                                                               Maximum transport speed                                                       (m/minute)                                                               Quantity   Transfer test                                                                            REL test                                      Compound  (% by      (surface   (complete                                     No.       weight)    curing)    curing)                                       ______________________________________                                        1         3          >170       120                                                     6          >170       >170                                          6         3          >170        80                                                     6          >170       160                                           7         3           160        80                                                     6          >170       170                                           8         3           150        90                                                     6          >170       130                                           10        3            60        20                                                     6           160        70                                           11        3            90        40                                                     6          >170       110                                           12        3            30        30                                                     6           120        60                                           14        3           140        70                                                     6           170       150                                           15        3          >170        90                                                     6          >170       >170                                          18        3            30        30                                                     6           130        60                                           20        3           130        70                                                     6          >170        90                                           21        3          >170        90                                                     6          >170       150                                           23        3           100        50                                                     6          >170       110                                           ______________________________________                                    

EXAMPLE 2

The concomitant use of the thioxanthones as sensitisers.

A white lacquer is prepared in accordance with the followingformulation:

17.6 g of Ebecryl®593 (polyester acrylate resin made by UCB, Belgium)

11.8 g of N-vinylpyrrolidone,

19.6 g of titanium dioxide RTC-2 (titanium dioxide made by Tioxide,England),

19.6 g of Sachtolith®HDA (lithopone made by Sachtleben Chemie, WestGermany),

11.8 g of trimethylolpropane trisacrylate and

19.6 g of Setalux®UV 2276 (acrylated epoxide resin based on bisphenol A,Kunstharzfabrik Synthese, Holland).

The above components, together with 125 g of glass beads (diameter 4 cm)are ground to a particle size ≦5 μm in a 250 ml glass bottle for atleast 24 hours.

The stock paste thus obtained is divided into portions and each portionis mixed with the photoinitiators and photosensitisers (co-initiators)indicated in Table 3, by stirring at 60° C., and the mixtures are groundwith glass beads for a further 16 hours.

The white lacquers thus prepared are applied to sheets of glass in athickness of 30 μm, using a doctor blade. The samples are exposed tolight in a single passage in a PPG irradiation apparatus with one or twolamps each having an output of 80 watt/cm. The speed of passage of thesamples through the irradiation apparatus is raised continuously untiladequate curing no longer takes place. The maximum speed of which alacquer film which is still resistant to wiping is formed, is shown inTable 3 as "rate of curing".

The following compounds are used in this test:

photoinitiator ##STR42## photosensitiser ##STR43##

                  TABLE 3                                                         ______________________________________                                        Photo-   Co-initiator                                                                              Rate of curing                                           initiator                                                                              (sensitiser)                                                                              80 W/cm  160 W/cm                                        ______________________________________                                        2% PI 1  --          10 m/min 10 m/min                                        2% PI 1  0,25% PS 1  30 m/min 70 m/min                                        2% PI 1  0,25% PS 2  20 m/min 40 m/min                                        2% PI 1  0,25% PS 3  70 m/min 150 m/min                                       2% PI 1  0,25% PS 4  90 m/min >170 m/min                                      ______________________________________                                    

It can be seen from the table that even small quanttities of thesensitiser accelerate the rate of curing considerably.

What is claimed is:
 1. A compound of the formula I ##STR44## in which Aris an oxygen-containing aromatic radical of the formula: ##STR45##wherein R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one another are eachhydrogen halogen, C₁ -C₄ -alkyl, C₃ -C₁₂ -alkenyl, C₅ -C₆ -cycloalkyl,phenyl, --OH or --OR⁹, with the proviso however that at least one of theradicals R⁴ to R⁸ is an --OR⁹ group,R⁹ is C₃ -C₁₂ -alkenyl, cyclohexyl,or hydroxycyclohexyl, X is morpholino or N(C₂ -C₄ alkyl substituted byC₁ -C₄ alkoxy)₂, R¹ and R² independently of one another are each C₁ -C₈-alkyl, or R¹ and R² together are C₅ -C₈ -alkylene,or an acid additionsalt of such a compound.
 2. A compound of the formula I according toclaim 1, wherein Ar is a phenyl radical which is substituted in the4-position by a group --OR⁹.
 3. A compound of the formula I according toclaim 1, wherein Ar is a phenyl radical substituted in the 4-position bya group --OR⁹, R⁹ is C₃ -C₆ -alkenyl or cyclohexyl, R¹ and R² are C₁ -C₄-alkyl, or R¹ and R² together are C₄ -C₅ -alkylene, and X is amorpholino radical or a radical of the formula --N(CH₂ CH₂ --OCH₃)₂. 4.A compound according to claim 1 of the formula ##STR46##